TWI697528B - Coating agent, film, layered product, surface protected articles - Google Patents

Abstract

The present invention obtains a coating agent that can form a surface layer with excellent self-repairing properties and antifouling properties by coating on the surface of a substrate (for example, thermoplastic polyurethane) and curing it. The coating agent of the present application includes (meth)acrylate urethane resin (a), fluorine-based compound (b), and photopolymerization initiator (d). The (meth)acrylate urethane resin (a) has a weight average molecular weight (Mw) of 10,000 to 800,000. The fluorine-based compound (b) has at least two polymerizable functional groups. The surface layer formed by the coating agent has excellent self-healing properties, antifouling properties, and extensibility for damages.

Description

Coating agent, film, laminate, surface protection article

The present invention relates to a coating agent. In particular, it relates to a coating agent that can be applied to a substrate and cured to form a laminate with excellent self-repairing and antifouling properties.

Since the past, thermoplastic polyurethane (TPU) with high impact strength has been used as a base material for protective films and the like. Especially in Europe and the United States, a film that protects the car body from splashing stones or damage is widely used under the name of Paint Protection Film (PPF). For example, there is 3M's Scotchgard Paint Protection Film (Scotchgard Paint Protection Film).

As a protective film using a thermoplastic polyurethane, Patent Document 1 discloses a multilayer film for protecting the surface, especially for protecting the surface (for example, car, airplane, ship, etc.) Coated) film, and more specifically, such as a multilayer protective film with a polyurethane layer on the uppermost part of the thermoplastic polyurethane layer (paragraph 0001). The coating surface of the car body part of the ride is protected by a multilayer protective film.

These protective films are typically aimed at protecting the surface of the article from external factors and preventing damage to the article. In recent years, the following protective films have been further needed: In addition to the protective article, it has the self-repairing property of disappearing the damage of the protective film itself even if the protective film is damaged, and the antifouling property of preventing the adhesion of dirt.

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 2008-539107

Therefore, the subject of the present invention is to provide a coating agent that can form a laminate with excellent self-repairing and antifouling properties by coating on the surface of a substrate (for example, thermoplastic polyurethane) and curing it .

The inventors of the present invention have made diligent studies to solve the above-mentioned problems. As a result, it was found that the surface layer formed by the coating agent containing the (meth)acrylate urethane resin (a) and the fluorine-based compound (b) having a polymerizable functional group has a (meth) The combination of an acrylic urethane resin and a fluorine compound is excellent in self-healing properties, antifouling properties, and further extensibility, thereby completing the present invention.

The coating agent of the first aspect of the present invention includes (meth)acrylate urethane resin (a), fluorine-based compound (b), and photopolymerization initiator (d), and (meth)acrylic amine The carbamate-based resin (a) has a weight average molecular weight (Mw) of 10,000 to 800,000, and the fluorine-based compound (b) has at least two polymerizable functional groups.

With such a configuration, it becomes a coating agent that can form a surface layer excellent in damaged self-repairing properties, antifouling properties, and extensibility. That is, if the coating agent is applied to the substrate film etc. To form a coating film (before hardening), the fluorine-based compound (b) accumulates on the surface of the layer (refer to fc in FIG. 1). Furthermore, when the coating film is cured, the (meth)acrylate urethane-based resin (a) and the fluorine-based compound (b) having a polymerizable functional group are mutually cross-linked. The formed surface layer is immobilized by cross-linking, which can inhibit the penetration of dirt and has excellent antifouling properties, as well as prevent exudation and increase the durability of antifouling properties. Further, the use of (meth)acrylate urethane resin The flexibility of (a), the self-repair of damage, and the elongation are also excellent.

In the coating agent of the second aspect of the present invention, in the coating agent of the first aspect of the present invention, the fluorine-based compound (b) is a perfluoropolyether having a (meth)acryloyl group. The so-called "(meth)acryloyl group" refers to an acryloyl group or a methacryloyl group.

With this structure, the radically polymerizable (meth)acrylic group can easily form a crosslink of the (meth)acrylate urethane resin (a) and the fluorine compound (b) .

The coating agent of the third aspect of the present invention is in the coating agent of the first or second aspect of the present invention, with respect to the (meth)acrylate urethane resin (a) and The total amount of the fluorine-based compound (b) contains 1 wt% (weight percent) to 9 wt% of the fluorine-based compound (b).

If configured in this way, the (meth)acrylate urethane resin (a) and the fluorine-based compound (b) are contained in an appropriate ratio, and the self-healing property, antifouling property, and extensibility are particularly excellent Coating agent for the surface layer.

The coating agent of the fourth aspect of the present invention is the coating agent of any one of the first to third aspects of the present invention, and further contains fluorosilsesquioxane (fluorosilsesquioxane) derivative (c), and the fluorosilsesquioxane derivative (c) has at least one polymerizable functional group.

With such a configuration, it becomes a coating agent that can form a surface layer with improved antifouling properties and excellent smoothness.

The coating agent of the fifth aspect of the present invention is that in the coating agent of the fourth aspect of the present invention, the fluorosilsesquioxane derivative (c) is a cage structure fluorosilsesquioxane .

If configured in this way, the cage structure fluorosilsesquioxane has the property of being more likely to accumulate on the interface with the air, and when the coating agent is applied to the substrate film, etc., the accumulation of the Speed on the interface.

The coating agent of the sixth aspect of the present invention is based on the coating agent of the fourth or fifth aspect of the present invention, with respect to the (meth)acrylate urethane resin (a), The total amount of the fluorine-based compound (b) and the fluorosilsesquioxane derivative (c) contains 0.1 wt% to 10 wt% of the fluorosilsesquioxane derivative (c).

If configured in this way, the (meth)acrylate urethane resin (a), the fluorine compound (b), and the fluorosilsesquioxane derivative (c) are contained in an appropriate ratio, and it can be formed into self It is a coating agent for surface layers with particularly excellent repairability, antifouling properties, elongation, and smoothness.

The film of the seventh aspect of the present invention is a film obtained by curing the coating agent of any one of the first aspect to the sixth aspect of the present invention.

With such a configuration, the obtained cured film becomes a film having self-repairing properties, antifouling properties, extensibility, and smoothness possessed by the surface layer.

The laminate of the eighth aspect of the present invention is, for example, as shown in FIGS. 1 and 2, and includes: a base film 11 formed of thermoplastic polyurethane; and a surface layer 12, by making the second The coating agent of any one of the first aspect to the sixth aspect is formed by curing on the first surface side of the base film 11. In addition, in this specification, the term "on the surface side" means that the layer can be laminated by contact or can be laminated through other layers. In Fig. 1, s1 represents the surface, and in Fig. 2, ss represents the fluorosilsesquioxane derivative.

With this configuration, the laminate has the self-healing properties, antifouling properties, extensibility, and smoothness of the surface layer, as well as the flexibility of the thermoplastic polyurethane of the base film. Layered body.

The laminate of the ninth aspect of the present invention is the laminate of the eighth aspect of the present invention. For example, as shown in FIGS. 1 and 2, an adhesive layer is provided on the side opposite to the first surface side of the base film 11 13. A release film 14 is provided on the surface of the adhesive layer 13 opposite to the base film 11, and the adhesive layer contains at least one resin selected from the group consisting of acrylic, urethane, rubber, and silicone , And at least one release agent selected from the group consisting of fluorine resin, silicone resin, and long-chain urethane is applied to the surface of the release film facing the adhesive layer.

With such a configuration, it is easy to peel the release film from the adhesive layer.

The surface protection article of the tenth aspect of the present invention includes: the laminate of the eighth or ninth aspect of the present invention from which the peeling film is peeled; and the peeling film is peeled by the adhesive layer The laminated body is attached to the surface of the article.

If configured in this way, the surface can be protected from damage and the like by thermoplastic polyurethane having high impact strength. In addition, even if Yu Yin becomes the most superficial surface When the layer is damaged, it can be self-repaired, and the outermost surface is also excellent in antifouling, elongation, and smoothness.

According to the coating agent of the invention of the present application, a surface layer with excellent antifouling properties for preventing the adhesion of dirt and self-repairing properties for eliminating damage when damaged can be formed on the base film. As a result, when the base film is formed of thermoplastic polyurethane, in addition to the flexibility of thermoplastic polyurethane, it is possible to form a laminate that is excellent in self-repairing and antifouling properties. The body can protect the surface of the object to be adhered.

11: Base film

12: Surface layer

13: Adhesive layer

14: peeling film

100, 200: layered body

fc: fluorine compound

s1: surface

ss: fluorosilsesquioxane derivative

Fig. 1 is a diagram showing the layer structure of a laminate 100 according to a second embodiment of the present invention.

FIG. 2 is a diagram showing the layer structure of a laminate 200 according to the second embodiment of the present invention.

This application is based on Japanese Patent Application No. 2015-074274 filed in Japan on March 31, 2015, and its content forms a part of the content of this application. The present invention can be more fully understood by the following detailed description. The further application scope of the present invention will become clear by the following detailed description. However, detailed description and specific examples are ideal embodiments of the present invention, and are described only for description. The reason is that it is clear to practitioners in this field that Various changes and changes can be made from this detailed description within the spirit and scope of the present invention. The applicant does not intend to dedicate any of the recorded implementation forms to the public, and changes and substitutions that may not be included in the scope of the patent application are also part of the invention under the theory of equality.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. In addition, in each figure, the same or similar parts are denoted by the same or similar symbols, and repeated descriptions are omitted. In addition, the present invention is not limited by the following embodiments.

[Coating agent]

The coating agent of the first embodiment of the present application includes (meth)acrylate urethane resin (a), fluorine-based compound (b), and photopolymerization initiator (d), (meth) The acrylic urethane-based resin (a) has a weight average molecular weight (Mw) of 10,000 to 800,000, and the fluorine-based compound (b) has at least two polymerizable functional groups. For example, as shown in FIG. 1, when a coating agent is applied to the base film 11 and cured, a surface layer 12 excellent in self-healing properties, antifouling properties, and extensibility can be formed.

Furthermore, the coating agent may further contain a fluorosilsesquioxane derivative (c). The fluorosilsesquioxane derivative (c) has at least one polymerizable functional group. With the fluorosilsesquioxane derivative (c), the antifouling property of the surface layer can be improved, and excellent smoothness can be imparted.

In addition, the coating agent may further contain a solvent (e) and an additive (f).

[(Meth)acrylate urethane resin (a)]

The (meth)acrylate urethane resin (a) is an active energy ray curable resin having a (meth)acrylic acid group and a urethane skeleton, for example, purple External curable resin. The (meth)acrylate urethane resin (a) imparts flexibility (flexibility) to the surface layer.

The (meth)acrylic urethane-based resin (a) can also be a polyol-based compound (polyisocyanate) having a plurality of isocyanate groups in one molecule and a polyol having two or more hydroxyl groups. Compounds (polyhydroxy compounds or polyols) are reacted, and then hydroxyl-containing (meth)acrylate compounds are reacted to obtain radically polymerizable unsaturated group-containing oligomers, prepolymers, polymerization Things.

In particular, a polycarbonate-based (meth)acrylate urethane using a polycarbonate polyol as a polyhydroxy compound is preferred. By using polycarbonate-based (meth)acrylate urethane, the formed surface layer can have excellent stretchability and toughness.

Alternatively, a polyester-based (meth)acrylate urethane using polyester polyol as the polyhydroxy compound is also preferable. By using polyester-based (meth)acrylate urethane, the formed surface layer can have excellent stretchability and toughness.

Specific examples of the polyisocyanate include: 2,4-toluene diisocyanate and its isomers, diphenylmethane diisocyanate, hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, and isophor Ketone diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, Burnock D-750 (trade name: DIC) (Stock) ), Crisvon (Crisvon) NK (trade name: manufactured by Di Aisheng (Stock)), Desmodur L (trade name: residential Sumitomo Bayer Urethane (manufactured by shares), Coronate L (trade name: manufactured by Nippon Polyurethane Industry (shares)), tower Takenate D102 (trade name: Mitsui Takeda Chemicals (manufactured by Mitsui Takeda Chemicals)), Isonate 143L (trade name: Mitsubishi Chemical Co., Ltd.), etc.

Examples of the polyhydroxy compound include polycarbonate polyols, polyester polyols, polyether polyols, polycaprolactone polyols, and the like. Specifically, glycerol-ethylene oxide adducts, Glycerin-propylene oxide adduct, glycerin-tetrahydrofuran adduct, glycerin-ethylene oxide-propylene oxide adduct, trimethylolpropane-ethylene oxide adduct, trimethylolpropane- Propylene oxide adduct, trimethylolpropane-tetrahydrofuran adduct, trimethylolpropane-ethylene oxide-propylene oxide adduct, dipentaerythritol-ethylene oxide adduct, dipentaerythritol- Propylene oxide adduct, dipentaerythritol-tetrahydrofuran adduct, dipentaerythritol-ethylene oxide-propylene oxide adduct, etc.

As the polyols, specifically, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 2-methyl-1,3- Propylene glycol, 1,3-butanediol, adducts of bisphenol A and propylene oxide or ethylene oxide, 1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane, 1, 2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, p-xylene glycol, dicyclohexyl-4,4-diol, 2,6-decahydronaphthalenediol , 2,7-Decahydronaphthalenediol, etc.

The hydroxyl group-containing (meth)acrylate compound is not particularly limited, but it is preferably a hydroxyl group-containing (meth)acrylate compound. Specifically, for example, Examples: 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono (Meth)acrylate, di(meth)acrylate of tris(hydroxyethyl)isocyanuric acid, pentaerythritol tri(meth)acrylate, etc.

The (meth)acrylate urethane resin (a) can be synthesized by a known method. As an example, it can be obtained by reacting a predetermined amount of organic polyisocyanate (a-1) and polycarbonate polyol (a-2) at 70°C to 80°C until isocyanate remains After the concentration becomes a predetermined amount, a predetermined amount of (meth)acrylate (a-3) containing one or more hydroxyl groups in the molecule is added, and a polymerization inhibitor (such as hydroquinone monomethyl ether) is added. In the presence of ), the reaction is carried out at 70°C to 80°C until the residual isocyanate concentration becomes 0.1wt% or less.

The weight average molecular weight (Mw) of the (meth)acrylate urethane resin (a) is 10,000 to 800,000, preferably in the range of 50,000 to 500,000. By setting it as this range, flexibility can be imparted to the surface layer. In the case of 10,000 or more, the crosslink density in the surface layer will not become too high.

[Fluorine-based compound (b)]

The fluorine-based compound (b) may be any of monomers, oligomers, prepolymers, and polymers as long as it has at least two polymerizable functional groups. For example, as the fluorine-based compound (b), perfluoropolyether having a (meth)acryloyl group can be cited. In addition, in this application, when it is called a fluorine-based compound (b), the following fluorosilsesquioxane derivative (c) is not included.

As the perfluoropolyether, for example, one having a structure in which a divalent fluorinated carbon group having 1 to 3 carbon atoms is alternately connected with an oxygen atom is mentioned. The divalent fluorocarbon group having 1 to 3 carbon atoms may be one type or a combination of two or more types.

Specific examples of the perfluoropolyether include those represented by the following formula (1).

In the above formula (1), X is the following formula (1-1) to formula (1-5). In addition, X may be any of the following formulas (1-1) to (1-5), or may have two or more of the following formulas (1-1) to (1-5). For example, as the X, a structure represented by -(CF ₂ CF ₂ -O) _n -(CF ₂ -O) _n -can be cited as having the following formulas (1-1) to (1-5) ) In two or more structures. When two or more structures represented by formula (1-1) to formula (1-5) are contained as the X, it may also have a random structure or a block structure including a structural unit of -(XO)- . In addition, n is an integer of 2 to 200 representing a repeating unit.

[化2]

The fluorine-based compound (b) preferably has a polymerizable functional group at least at both ends. The polymerizable functional group is not particularly limited as long as it is a group that undergoes radical polymerization, and includes, for example, methacryloyl, acryloyl, allyl, styryl, α-methylstyryl, and vinyl. Base, vinyl ether, vinyl ester, acrylamide, methacrylamide, N-vinylamide, maleate, fumarate, N-substituted maleic amide Among them, amines and the like are preferably groups containing (meth)acrylic or styryl groups. Here, (meth)acrylic acid is a general term of acrylic acid and methacrylic acid, and means acrylic acid and/or methacrylic acid.

The fluorine-based compound (b) can be synthesized by a known method.

The content of the fluorine compound (b) is preferably 1wt%-9wt%, more preferably 1wt% relative to the total amount of the (meth)acrylate urethane resin (a) and the fluorine compound (b) ~7wt%. If it is 1 part by weight or more, the surface layer can be sufficiently If the antifouling property is 9wt% or less, the flexibility of the surface layer and poor self-repairing properties can be avoided.

[Fluorossesquioxane derivatives (c)]

The fluorosilsesquioxane derivative (c) may be any of monomers, oligomers, prepolymers, and polymers as long as it has at least one polymerizable functional group.

. Fluorosilsesquioxane monomer

Silsesquioxane is a general term for polysiloxane represented by [(R-SiO _1.5 )n] (R is an arbitrary substituent). The structure of the silsesquioxane corresponds to its Si-O-Si framework, and is generally classified into a random structure, a ladder structure, and a cage structure. Furthermore, the cage structure is classified into T8 type, T10 type, T12 type, etc. according to the amount of Si contained.

The fluorosilsesquioxane should just have the property of being easy to accumulate on the interface between air and solid (or liquid) in a hydrophobic environment (for example, in air). As long as it is fluorosilsesquioxane accumulated on the interface, the effect of the invention of this application can be fully exhibited. Due to the excellent surface aggregation properties of such fluorosilsesquioxane, the surface modification of the surface layer 12 can be performed in a small amount and effectively.

As an example of fluorosilsesquioxane, fluorosilsesquioxane having a molecular structure represented by the following formula (2) can be cited.

[化3]

That is, among the random structure, ladder structure, and cage structure as the structure of silsesquioxane, the cage structure is particularly preferable. If fluorosilsesquioxanes with a cage structure are used, compared with fluorosilsesquioxanes of other structures, the rate of aggregation on the interface can be increased.

In consideration of ease of availability, it is preferably any of T8 type, T10 type, and T12 type.

The substituent (R) in the formula [(R-SiO _1.5 )n] is preferably a fluoroalkyl group (R _f ). In consideration of solubility in solvents, the carbon number of R _f is preferably 1-8. R _f may be a linear group or a branched group. Specifically, as a linear group, -CH ₂ CH ₂ CF ₃ , -CH ₂ CH ₂ CF ₂ CF ₃ , -CH ₂ CH ₂ CF ₂ CF ₂ CF ₃ , -CH ₂ CH ₂ CF ₂ CF ₂ CF ₂ CF ₃ , -CH ₂ CH ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₃ , -CH ₂ CH ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₂ CF ₃ , as the branched group, -CH ₂ CH ₂ CF(CF ₃ ) ₂ , -CH ₂ CH(CF ₃ )CF ₂ CF ₃ , -CH(CF ₃ )CH ₂ CF ₂ CF ₃ , -CH ₂ C(CF ₃ ) ₂ CF ₃ , -C (CF ₃ ) ₂ CH ₂ CF ₃ -CH ₂ CH ₂ CF ₂ CF(CF ₃ ) ₂ 、-CH ₂ CH ₂ CF(CF ₃ )CF ₂ CF ₃ 、-CH ₂ CH ₂ C(CF ₃ ) ₂ CF ₃ etc. Furthermore, R _f may be different groups, or all the same groups.

In the above formula (2), fluorosilsesquioxane having "3-(methacryloxy)propyl group" in one Si is exemplified, but it is not limited to this polymerizable functional group. For example, when the position of the "3-(methacryloxy)propyl group" is set to Z, the position can be substituted with another functional group. Specifically, as Z, it can be hydrogen, hydroxyl, alkenyl, or halogen (chlorine, bromine, iodine), alkoxy, phenoxy, polyalkyleneoxy, -COOH, 2-oxapropane- 1,3-diol, alkoxycarbonyl, alkenyloxycarbonyl, oxetanyl, 3,4-epoxycyclohexyl, oxetanyl, oxetanyl, -NH-,- NH ₂ , -CN, -NCO, alkynyl, cycloalkenyl, acryloxy, methacryloxy, urethane acryl, carbamate methacryl, -SH And any base of -PH ₂ . Further, as Z, it can be set via the alkylene group (hydro ~ -PH _2). The alkylene group bonded to Si is not particularly limited, but it is preferably an alkylene group having 1 to 8 carbon atoms, and particularly preferably an alkylene group having 3 carbon atoms. However, a group having an alkoxy group, a group having a halogenated sulfonyl group, and a group having an α-haloester group are not included in the selection range.

Among them, particularly preferred is fluorosilsesquioxane in which at least two polymerizable functional groups are bonded to Si. For example, in the above formula (2), the fluorosilsesquioxane having "3-(methacryloxy)propyl" in one Si is exemplified, but it is more preferable than the other one Among the above Si, the fluorosilsesquioxane having the "3-(methacryloxy) propyl group". Furthermore, the polymerizable functional group is preferably a radical polymerizable functional group.

. Fluorossesquioxane oligomers, prepolymers, polymers

Hereinafter, fluorosilsesquioxane oligomers, prepolymers, and polymers are collectively referred to as fluorosis Semi-siloxane polymer.

When the functional group is a polymerizable group, the fluorosilsesquioxane polymer can be a homopolymer of fluorosilsesquioxane, or it can be combined with other general monomers (such as addition polymerizable Monomer) copolymer. It may also be a copolymer of fluorosilsesquioxanes having different polymerizable groups. In this case, any known method can be adopted as the method of polymerization. In this way, the fluorosilsesquioxane used in the coating agent of the present application may also be a fluorosilsesquioxane polymer.

However, the fluorosilsesquioxane polymer after polymerization has at least one polymerizable functional group. Furthermore, the polymerizable functional group is preferably a radical polymerizable functional group.

That is, the fluorosilsesquioxane of the formula (2) may have an addition polymerizable functional group as Z. Alternatively, it may have an addition polymerizable functional group as Z via an alkylene group. Examples of addition polymerizable functional groups include: groups having terminal olefin type or internal olefin type radical polymerizable functional groups; groups having cationically polymerizable functional groups such as vinyl ether and propenyl ether; and groups having ethylene It is an anionic polymerizable functional group such as a carboxyl group and a cyanoacryloyl group, but a radical polymerizable functional group is preferable.

The radically polymerizable functional group is not particularly limited as long as it is a radically polymerizable group, and includes, for example, a methacryl group, an acryl group, an allyl group, a styryl group, and an α-methyl styryl group. , Vinyl, vinyl ether, vinyl ester, acrylamide, methacrylamide, N-vinylamide, maleate, fumarate, N-substituted maleate Among them, a group containing a (meth)acrylic acid or a styryl group is preferable for imines and the like. Here, (meth)acrylic acid is acrylic acid and methacrylic acid The general term for acid refers to acrylic acid and/or methacrylic acid.

Examples of the radically polymerizable functional group having the (meth)acrylic acid include a group represented by the following formula (3). In formula (3), Y ¹ represents an alkylene group having 2 to 10 carbon atoms, preferably represents an alkylene group having 2 to 6 carbon atoms, and more preferably represents a propylene group. In addition, X represents hydrogen or an alkyl group having 1 to 3 carbon atoms, and preferably represents hydrogen or methyl.

In addition, examples of the radically polymerizable functional group having the styryl group include a group represented by the following formula (4). In the formula (4), Y ² represents a single bond or an alkylene group having 1 to 10 carbon atoms, preferably represents a single bond or an alkylene group having 1 to 6 carbon atoms, and more preferably represents a single bond or an ethylene group. In addition, the vinyl group is bonded to any carbon of the benzene ring, and is preferably bonded to the para-position carbon relative to Y ² .

The addition polymerizable monomer includes an addition polymerizable monomer having a crosslinkable functional group and an addition polymerizable monomer having no crosslinkable functional group. The addition polymerizable monomer having a crosslinkable functional group may be a compound having one or more addition polymerizable double bonds, for example, a vinyl compound or a vinylidene compound Either a compound or a vinylidene compound, more specifically, a (meth)acrylic compound, a styrene compound, etc. can be illustrated.

Examples of the (meth)acrylic compound include (meth)acrylic acid and (meth)acrylic acid esters, as well as (meth)acrylamide, (meth)acrylonitrile, and the like.

As an example of the (meth)acrylic compound of the addition polymerizable monomer, there is a (meth)acrylate having a crosslinkable functional group. Examples of the crosslinkable functional group include epoxy groups such as glycidyl and epoxycyclohexyl, oxetanyl, isocyanate, acid anhydride, carboxyl, and hydroxyl groups, etc., and epoxy groups such as glycidyl are preferred. Group or oxetanyl. Specific examples of the (meth)acrylate having a crosslinkable functional group include: (meth)acrylic acid, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc. (Meth)acrylic acid hydroxyalkyl ester; (meth)acrylate containing epoxy group such as glycidyl (meth)acrylate; alicyclic containing ring such as 3,4-epoxycyclohexyl methyl (meth)acrylate Oxy (meth)acrylate; 3-ethyl-3-(meth)acryloyloxymethyloxetane and other oxetanyl-containing (meth)acrylates; isocyanic acid 2-(meth)acryloyloxy ethyl; γ-(methacryloyloxypropyl)trimethoxysilane; (meth)acrylic acid-2-aminoethyl, (meth)acrylic acid 2- (2-Bromopropionyloxy)ethyl, 2-(2-bromoisobutyroxy)ethyl (meth)acrylate; 1-(meth)propenyloxy-2-phenyl-2- (2,2,6,6-Tetramethyl-1-piperidinyloxy)ethane, 1-(4-((4-(meth)propenyloxy)ethoxyethyl)phenyl ethyl Oxy)piperidine, (meth)acrylate 1,2,2,6,6-pentamethyl-4-piperidine ester, (meth)acrylate 2,2,6,6-pentamethyl-4- Piperidinate and others.

Examples of the styrene compound having one addition polymerizable double bond include a styrene compound having a crosslinkable functional group. Specific examples of the crosslinkable functional group Including epoxy groups such as glycidyl groups, oxetanyl groups, halogens, amino groups, isocyanate groups, acid anhydrides, carboxyl groups, hydroxyl groups, thiol groups, silanoxy groups, etc.

Examples of styrene compounds having crosslinkable functional groups include o-aminostyrene, p-styrene chlorosulfonic acid, styrene sulfonic acid and its salts, vinyl phenyl methyl dithiocarbamate, 2 -(2-Bromopropionyloxy)styrene, 2-(2-bromoisobutyroxy)styrene, 1-(2-((4-vinylphenyl)methoxy)-1-benzene Ethoxy)-2,2,6,6-tetramethylpiperidine, or a compound represented by the following formula.

[化5]

In addition to the addition polymerizable monomer, in order to control the compatibility with the curable resin, leveling properties, the amount of crosslinkable functional groups in the copolymer, etc., the addition polymerizability may be used in combination as necessary Addition polymerizable monomers other than monomers.

Examples of the addition polymerizable monomer having no crosslinkable functional group include (meth)acrylic compounds having one addition polymerizable double bond and no crosslinkable functional group, and one Form polymerizable double bonds, and do not have crosslinkable functional groups 的styrene compound. Specific examples of the (meth)acrylic compound include: methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, (meth) Butyl acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, ( N-heptyl (meth)acrylate, n-octyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, decyl (meth)acrylate, (meth)acrylic acid Alkyl (meth)acrylates such as lauryl ester and stearyl (meth)acrylate; aryl (meth)acrylates such as phenyl (meth)acrylate and toluene (meth)acrylate; (Meth) benzyl acrylate and other (meth) aryl alkyl esters; 2-methoxyethyl (meth)acrylate, 3-methoxypropyl (meth)acrylate, (meth)acrylic acid Alkoxyalkyl (meth)acrylates such as 3-methoxybutyl ester; ethylene oxide adducts of (meth)acrylic acid, etc.

Specific examples of the (meth)acrylic compound having one addition polymerizable double bond and not having a crosslinkable functional group further include: trifluoromethyl methyl (meth)acrylate, (meth)acrylic acid 2-Trifluoromethyl ethyl, 2-perfluoroethyl ethyl (meth)acrylate, 2-perfluoroethyl-2-perfluorobutyl ethyl (meth)acrylate, (meth)acrylate Fluoroethyl, trifluoromethyl (meth)acrylate, diperfluoromethyl methyl (meth)acrylate, 2-perfluoromethyl-2-perfluoroethyl ethyl (meth)acrylate, (meth)acrylate Fluoroalkyl (meth)acrylates such as 2-perfluorohexylethyl acrylate, 2-perfluorodecylethyl (meth)acrylate, and 2-perfluorohexadecylethyl (meth)acrylate Wait.

Furthermore, examples of the (meth)acrylic compound having one addition polymerizable double bond and not having a crosslinkable functional group include a (meth)acrylic compound having a silsesquioxane skeleton. Specific examples of the (meth)acrylic compound having a silsesquioxane skeleton include: (meth)acrylic acid 3-(3,5,7,9,11,13,15-heptaethyl pentacyclic [9.5. 1.1 ^{3,9.1 5,15} .1 ⁷ ,: ¹³ ) octasiloxane-1-yl)propyl ester, (meth)acrylic acid 3-(3,5,7,9,11,13,15- Heptaisobutyl-pentacyclo[9.5.1.1 ^{3,9.1 5,15.1 7,13} ] octasiloxane-1-yl) propyl ester, (meth)acrylic acid 3-(3,5,7 ,9,11,13,15-Heptaisooctyl pentacyclic [9.5.1.1 ^{3,9.1 5,15} .1 ^7,13 ] octasiloxane-1-yl)propyl, (meth)acrylic acid 3-(3,5,7,9,11,13,15-Heptacyclopentyl pentacyclic [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ] octasiloxane-1-yl) Propyl ester, (meth)acrylic acid 3-(3,5,7,9,11,13,15-heptaphenyl pentacyclic [9.5.1.1 ^{3,9.1 5,15} .1 ^7,13 ] octasil (Oxyalkyl-1-yl) propyl ester, (meth)acrylic acid 3-[(3,5,7,9,11,13,15-heptaethyl pentacyclic [9.5.1.1 ^{3,9.1 5,15} .1 ^7,13 ]octasiloxane-1-yloxy)dimethylsilyl]propyl ester, (meth)acrylic acid 3-[(3,5,7,9,11,13,15-seven Isobutyl pentacyclic [9.5.1.1 ^{3,9.1 5,15} .1 ^7,13 ] octasiloxane-1-yloxy)dimethylsilyl]propyl ester, (meth)acrylic acid 3- [(3,5,7,9,11,13,15-Heptaisooctyl pentacyclic [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ] octasiloxane-1-yloxy )Dimethylsilyl]propyl ester, (meth)acrylic acid 3-[(3,5,7,9,11,13,15-heptacyclopentyl pentacyclic [9.5.1.1 ^{3,9.1 5, 15.1 7,13]} silicon eight oxo-1-yloxy) dimethyl silicon alkyl] propyl (meth) acrylate, 3 - [(3,5,7,9,11,13,15- Heptaphenyl pentacyclic [9.5.1.1 ^{3,9.1 5,15.1 7,13} ] octasiloxane-1-yloxy)dimethylsilyl]propyl ester and the like. Specific examples of the styrene compound having one addition polymerizable double bond and not having a crosslinkable functional group include: styrene, vinyl toluene, α-methylstyrene, p-chlorostyrene, and the like.

As an example of the styrene compound having one addition polymerizable double bond and not having a crosslinkable functional group, a styrene compound containing silsesquioxane is further included. Examples of styrene derivatives containing silsesquioxane include: 1-(4-vinylphenyl)-3,5,7,9,11,13,15-heptaethyl pentacyclic [9.5.1.1 ^{3, 9} .1 ^5,15 .1 ^7,13 ]octasiloxane, 1-(4-vinylphenyl)-3,5,7,9,11,13,15-heptaisobutyl pentacyclic [9.5 .1.1 ^{3,9.1 5,15} .1 ^7,13 ]octasiloxane, 1-(4-vinylphenyl)-3,5,7,9,11,13,15-heptaisooctyl Pentacyclic [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ] octasiloxane, 1-(4-vinylphenyl)-3,5,7,9,11,13,15- seven cyclopentyl pentacyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] siloxane eight silicon, and 1- (4-vinylphenyl) -3,5,7,9,11 , 13,15- seven phenyl pentacyclo [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13] and the like having eight silicon alumoxane eight silicon alumoxane is 4-vinylphenyl (T8 type sesqui Siloxane); and 3-(3,5,7,9,11,13,15-heptaethyl pentacyclic [9.5.1.1 ^{3,9.1 5,15} .1 ^7,13 ] octasiloxane -1-yl) ethyl styrene, 3-(3,5,7,9,11,13,15-heptaisobutyl pentacyclic [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ] Octasiloxane-1-yl) ethyl styrene, 3-(3,5,7,9,11,13,15-heptaisooctyl pentacyclic [9.5.1.1 ^{3,9.1 5,15} .1 ^7,13 ]octasiloxane-1-yl)ethylstyrene, 3-(3,5,7,9,11,13,15-heptacyclopentyl pentacyclic [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ] octasiloxane-1-yl) ethyl styrene, 3-(3,5,7,9,11,13,15-heptaphenyl pentacyclic [9.5. 1.1 ^{3,9.1 5,15} .1 ^7,13 ]octasiloxane-1-yl)ethyl styrene, 3-((3,5,7,9,11,13,15-heptaethyl Pentacyclic [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ] octasiloxane-1-yloxy)dimethylsilyl)ethyl styrene, 3-((3,5, 7,9,11,13,15-Heptaisobutyl pentacyclic [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ]octasiloxane-1-yloxy)dimethylsilyl ) Ethyl styrene, 3-((3,5,7,9,11,13,15-heptaisooctyl pentacyclic [9.5.1.1 ^{3,9.1 5,15} .1 ^7,13 ] octasil Oxyalkyl-1-yloxy)dimethylsilyl)ethylstyrene, 3-((3,5,7,9 ,11,13,15-Heptacyclopentyl pentacyclic [9.5.1.1 ^{3,9.1 5,15} .1 ^7,13 ]octasiloxane-1-yloxy)dimethylsilyl)ethyl Styrene, and 3-((3,5,7,9,11,13,15-heptaphenyl pentacyclic [9.5.1.1 ^3,9 .1 ^5,15 .1 ^7,13 ] ^{octasiloxane-} 1-yloxy) dimethylsilyl group) ethyl styrene, etc., octasiloxane (T8 type silsesquioxane) having 4-vinylphenylethyl group.

Furthermore, as addition polymerizable monomers other than the above-mentioned addition polymerizable monomers, examples thereof include styrene, (meth)acrylates, silicones, and alkylene oxides, such as ethylene oxide. The main chain derived from alkane, propylene oxide, etc., and a macromolecular monomer with a polymerizable double bond.

Examples of addition polymerizable monomers also include compounds having two addition polymerizable double bonds. Examples of compounds having two addition polymerizable double bonds include: 1,3-butanediol=di(meth)acrylate, 1,4-butanediol=di(meth)acrylate, 1,6 -Hexanediol = di(meth)acrylate, polyethylene glycol = di(meth)acrylate, diethylene glycol = di(meth)acrylate, neopentyl glycol = di(meth)acrylic acid Ester, triethylene glycol = di(meth)acrylate, tripropylene glycol = di(meth)acrylate, hydroxytrimethyl acetate neopentyl glycol = di(meth)acrylate, trimethylol Propane=bis(meth)acrylate, bis[(meth)acryloxyethoxy]bisphenol A, bis[(meth)acryloxyethoxy]tetrabromobisphenol A, bis[ (Meth) acryloxy polyethoxy) bisphenol A, 1,3-bis(hydroxyethyl) 5,5-dimethylhydantoin, 3-methylpentanediol = bis(formaldehyde) Di(meth)acrylate of hydroxytrimethylacetate neopentyl glycol compound and bis((meth)acryloxypropyl]tetramethyldisiloxane, etc.) Meth) acrylate monomer, divinylbenzene.

Furthermore, it can also be exemplified that it has a main chain derived from styrene, (meth)acrylate, silicone, and alkylene oxide, such as ethylene oxide, propylene oxide, etc., and has two A macromolecular monomer with polymerizable double bonds.

Examples of addition polymerizable monomers also include compounds having three or more addition polymerizable double bonds. Examples of compounds having three or more addition polymerizable double bonds include: trimethylolpropane=tri(meth)acrylate, pentaerythritol=tri(meth)acrylate, pentaerythritol=tetra(meth)acrylate , Dipentaerythritol = monohydroxy penta (meth) acrylate, tris (2-hydroxyethyl isocyanate) = tris (meth) acrylate, tris (diethylene glycol) trimellitate = tris (methyl) Acrylate, 3,7,14-tris[(((meth)acryloxypropyl)dimethylsilyloxy)]-1,3,5,7,9,11,14-heptaethyl Tricyclic [7.3.3.1 ^5,11 ] heptasiloxane, 3,7,14-tris[(((meth)acryloxypropyl)dimethylsilyloxy)]-1,3,5 ,7,9,11,14-heptaisobutyl tricyclo[7.3.3.1 ^5,11 ] heptasiloxane, 3,7,14-tris[(((meth)acryloxypropyl) two Methylsilyloxy)]-1,3,5,7,9,11,14-heptaisooctyl tricyclo[7.3.3.1 ^5,11 ]heptasiloxane, 3,7,14-tri[( ((Meth)acryloxypropyl)dimethylsilyloxy)]-1,3,5,7,9,11,14-heptacyclopentyl tricyclo[7.3.3.1 ^5,11 ] seven Siloxane, 3,7,14-tris[(((meth)acryloxypropyl)dimethylsilyloxy)]-1,3,5,7,9,11,14-heptabenzene Base tricyclic [7.3.3.1 ^5,11 ] heptasiloxane, octa(3-(meth)acryloyloxypropyldimethylsilyloxy)octasesquioxane and octa(3-(methyl) Base) propylene oxypropyl) octasesquioxane.

Furthermore, it can also be exemplified that it has a main chain derived from styrene, (meth)acrylate, siloxane, and alkylene oxide, such as ethylene oxide, propylene oxide, etc., and has three or more polymerizable properties. Macromolecular monomers of double bonds.

The addition polymerizable monomer is preferably a (meth)acrylic compound, more preferably a (meth)acrylate, and still more preferably a lower alkyl group of (meth)acrylic acid (for example, carbon number 1 to 3) Esters or esters having crosslinkable functional groups, etc.

The polymer is an addition polymer of fluorosilsesquioxane or an addition copolymer with other addition polymerizable monomers. In the case of a copolymer, it can be a sequential copolymerization such as block copolymerization. The substance may also be a random copolymer, but is preferably a random copolymer. In addition, the polymer may have a cross-linked structure or a graft copolymer.

With respect to the total amount of (meth)acrylate urethane resin (a), fluorine compound (b), and fluorosilsesquioxane derivative (c), fluorosilsesquioxane derivative (c) The content of) is preferably 0.1wt%-10wt%, more preferably 0.1wt%-5wt%. If it is 0.1 wt% or more, the antifouling property of the surface layer can be improved and smoothness can be imparted, and if it is 10 wt% or less, it can avoid the deterioration of the softness of the surface layer and poor self-healing properties.

[Photopolymerization initiator (d)]

The photopolymerization initiator is not particularly limited. It is sufficient as long as it is an initiator that generates free radicals by active energy rays. For example, a phenalkyl ketone-based photopolymerization initiator and the like can be mentioned.

As a compound used as an active energy ray polymerization initiator, there are the following compounds: 1-hydroxycyclohexyl phenyl ketone, benzophenone, Michele ketone, 4,4'-bis(diethylamino ) Benzophenone, xanthone, thioxanthone, isopropyl xanthone, 2,4-diethyl thioxanthone, 2-ethylanthraquinone, acetophenone, 2-hydroxy -2-methylpropiophenone, 2-hydroxy-2-methyl-4'-isopropylpropiophenone, isopropyl benzoin ether, isobutyl benzoin ether, 2,2-diethoxyacetophenone, 2,2-Dimethoxy-2-phenylacetophenone, camphorquinone, benzoanthrone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane -1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)-butanone-1,4-dimethylaminobenzoic acid ethyl Ester, 4-Dimethylaminobenzoic acid isoamyl ester, 4,4'-bis(tertiary butyl peroxide) benzophenone, 3,4,4'-tris(tertiary butyl peroxide) Carbonyl) benzophenone, 2,4,6-trimethylbenzyl diphenyl phosphine oxide, 2-(4'-methoxystyryl)-4,6-bis(trichloromethyl) )-S-triazine, 2-(3',4'-dimethoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2',4'-bis Methoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 2-(2'-methoxystyryl)-4,6-bis(trichloromethyl)- S-triazine, 2-(4'-pentoxystyryl)-4,6-bis(trichloromethyl)-s-triazine, 4-[p-N,N-bis(ethoxycarbonylmethyl) ))-2,6-bis(trichloromethyl)-s-triazine, 1,3-bis(trichloromethyl)-5-(2'-chlorophenyl)-s-triazine, 1,3- Bis(trichloromethyl)-5-(4'-methoxyphenyl)-s-triazine, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethyl Amino styryl) benzothiazole, 2-mercaptobenzothiazole, 3,3'-carbonyl bis(7-diethylamino coumarin), 2-(o-chlorophenyl)-4,4' ,5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(4-ethoxycarbonyl) Phenyl)-1,2'-biimidazole, 2,2'-bis(2,4-dichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole , 2,2'-bis(2,4-dibromophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,4 ,6-Trichlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 3-(2-methyl-2-dimethylaminopropionyl) Carbazole, 3,6-bis(2-methyl-2-morpholinylpropionyl)-9-n-dodecylcarbazole, 1-hydroxycyclohexylphenyl ketone, bis(η5-2,4- Cyclopentadien-1-yl)-bis(2,6-difluoro-3-(1H-pyrrol-1-yl)-phenyl)titanium, 3,3',4,4'-tetra(peroxide Tertiary butylcarbonyl) benzophenone, 3,3',4,4'-tetra(tertiary hexyl peroxide) benzophenone, 3,3'-bis(methoxycarbonyl)-4, 4'-bis(tert-butyl carbonyl peroxide) benzophenone, 3,4'-bis(methoxycarbonyl)-4,3'-bis(tert-butyl carbonyl peroxide) benzophenone , 4,4'-bis(methoxycarbonyl)-3,3'-bis(tert-butyl carbonyl peroxide) benzophenone, 2-hydroxy-1-{4-[4-(2-hydroxyl 2-methyl-propanyl)-benzyl)phenyl)-2-methyl-propan-1-one, bis(2,4,6-trimethylbenzyl)-phenyl oxide phosphine. These compounds can be used singly, and it is also effective to use a mixture of two or more.

The content of the radical polymerization initiator is preferably 0.01 to 20 parts by weight with respect to the total amount (100 parts by weight) of the radical polymerizable resin. More preferably, it is 1 part by weight to 10 parts by weight.

[Solvent (e)]

The component (a), (b), (c), and (d) contained in the coating agent of the present application may be dissolved in a solvent such as an organic solvent and used. The solvent is not particularly limited. General organic solvents etc. can be used.

Specific examples of solvents include hydrocarbon-based solvents (benzene, toluene, etc.), ether-based solvents (diethyl ether, tetrahydrofuran, diphenyl ether, anisole, dimethoxybenzene, etc.), halogenated hydrocarbon-based solvents ( Dichloromethane, chloroform, chlorobenzene, etc.), ketone solvents (acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.), alcohol solvents (methanol, ethanol, propanol, isopropanol, butanol, Tertiary butanol, etc.), nitrile solvents (acetonitrile, propionitrile, benzonitrile, etc.), ester solvents (ethyl acetate, butyl acetate, methyl 2-hydroxyisobutyrate, etc.), carbonate-based solvents (carbonic acid Ethylene, propylene carbonate, etc.), amide-based solvents (N,N-dimethylformamide, N,N-dimethylacetamide), hydrochlorofluorocarbon-based solvents (HCFC-141b, HCFC-225), Hydrofluorocarbons (HFCs) solvents (HFCs with carbon number 2~4, 5 and 6 or more), Perfluorocarbon solvents (perfluoropentane, perfluorohexane), alicyclic hydrofluorocarbons Carbon-based solvents (fluorocyclopentane, fluorocyclobutane), oxygen-containing fluorine-based solvents (fluoroether, fluoropolyether, fluoroketone, fluoroalcohol), aromatic fluorine solvent (α, α, α-trifluoro Toluene, hexafluorobenzene), water. These solvents may be used alone, or two or more of them may be used in combination. For example, a mixed solvent of methyl ethyl ketone and methyl isobutyl ketone can be mentioned. By adding a solvent such as methyl ethyl ketone, which is expected to improve the solubility of the resin more than methyl isobutyl ketone, the workability of uniformizing the solution can be improved when the coating agent is formulated. In addition, by improving the solubility, the coating agent can be stabilized. The mixing ratio (weight basis) can utilize the range of methyl isobutyl ketone/methyl ethyl ketone=1~99/99~1, and the range of 20~80/80~20 is preferable, for example.

The content of the solvent is 20 parts by weight to 500 parts by weight with respect to the total amount (100 parts by weight) of the resin composition forming the cured film. Preferably it is 50 parts by weight to 400 parts by weight.

[Additive (f)]

In addition to the above, additives may also be added to the coating agent. For example, in order to impart hardness and scratch resistance to the film, a filler may be added. In order to improve coating properties, leveling agents can also be added. In addition, additives such as weathering agents and defoamers can also be added.

In more detail, the coating agent may further contain an active energy ray sensitizer, a polymerization inhibitor, and a polymerization initiation aid within a range that does not adversely affect the effect of the cured film formed by the coating agent. Agents, leveling agents, wettability modifiers, surfactants, plasticizers, ultraviolet absorbers, light stabilizers, antioxidants, antistatic agents, silane coupling agents, inorganic materials represented by silica or alumina Optional components such as fillers and organic fillers.

As an example of a leveling agent, commercially available acrylic surface conditioners BYK-350, BYK-352, BYK-354, BYK-356, BYK-381, BYK-392, BYK-394, BYK-3441, BYK-3440, BYK-3550 (all trade names: manufactured by BYK-Chemie. Japan (Stock)).

In addition, as silicone-based surface modifiers, examples include BYK-UV3500, BYK-UV-3570 (all trade names: manufactured by BYK Chemical Co., Ltd.), TEGO Rad 2100, 2200N, 2250, 2500, 2600, 2700 (all trade names: manufactured by Evonik Degussa Japan (Stock)), X-22-2445, X-22-2455, X-22-2457, X- 22-2458, X-22-2459, X-22-1602, X-22-1603, X-22-1615, X-22-1616, X-22-1618, X-22-1619, X-22- 2404, X-22-2474, X-22-174DX, X-22-8201, X-22-2426, X-22-164A, X-22-164C (all trade names: Shin-Etsu Chemical Co., Ltd.) )Wait.

Examples of weathering agents include: benzotriazoles, hydroxyphenyltriazines, benzophenones, salicylates, cyanoacrylates, triazines, or dibenzyl Resorcinol UV absorber.

Examples of benzotriazoles include TINUVIN PS, TINUVIN 99-2, TINUVIN 326, and TINUVIN manufactured by BASF. 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN Carboprotect, as examples of hydroxyphenyltriazines, Examples include TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 477, and TINUVIN 479 manufactured by BASF as the diphenyl form. Examples of ketones include 1413 manufactured by ADEKA and Sumisorb 130 manufactured by Sumika Chemtex. Examples of salicylic acid esters include phenyl salicylate and salicylic acid. P-tert-butylphenyl ester and p-octylphenyl salicylate. Examples of cyanoacrylates include 2-ethylhexyl 2-cyano-3,3-diphenyl acrylate and ethyl acrylate 2-cyano-3,3-diphenyl esters, as examples of triazines, LA-46 and LA-F70 manufactured by Adike, as examples of dibenzylresorcinols, 4,6-Dibenzylresorcinol etc. are mentioned.

These ultraviolet absorbers may be used alone, or multiple ultraviolet absorbers may be used in combination. As for the ultraviolet absorber, it is preferable to appropriately select the kind or combination according to the wavelength of ultraviolet rays to be absorbed.

In addition, as light stabilizers (Hindered Amine Light Stabilizer (Hindered Amine Light Stabilizer, HALS)), BASF's TINUVIN (registered trademark) 5100 (neutral type general HALS), TINUVIN 292 (compound name: bis(1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, methyl(1,2,2,6,6) -Pentamethyl-4-piperidinyl) sebacate), TINUVIN 152 (compound name: 2,4-bis[N-butyl-N-(1-cyclohexyloxy-2) ,2,6,6-Tetramethylpiperidin-4-yl)amino)-6-(2-hydroxyethylamine)-1,3,5-triazine), TINUVIN 144( Compound name: Bis(1,2,2,6,6-pentamethyl-4-piperidinyl)-[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl ] Methyl] butyl malonate), TINUVIN 123 (compound name: sebacic acid, bis(2,2,6,6-tetramethyl-1-(octyloxy)-4 -Piperidinyl) ester reaction product (in the presence of 1,1-dimethylethyl hydroperoxide and octane), TINUVIN 111FDL (about 50%, TINUVIN) 622. Compound name: (Succinic acid polymer (4-hydroxy-2,2,6,6-tetramethylpiperidinyl-base) in the presence of ethanol), about 50%, CHIMASSORB 119 , Compound name: N-N'-N"-N'''-Tetra(4,6-bis(butyl-(N-methyl-2,2,6,6-tetramethylpiperidine-4- (Amino) triazin-2-yl)-4,7-diazadecane-1,10-diamine), or Adekastab LA series manufactured by Adekastab Etc., specifically LA-52((5)-6116), LA-57((5)-5555), LA-62((5)-5711), LA-67((5)-5755), LA-82((5)-6023), LA-87((5)-6022). Furthermore, the existing chemical substance numbers are in parentheses.

As examples of inorganic fillers, commercially available products include: MEK-ST-40, MEK-ST-L, MEK-ST-ZL, PGM-AC-2140Y, PGM-AC-4130Y, manufactured by Nissan Chemical Industry AS-200, AS-520, anatase TiO ₂ , Al ₂ O ₃ , ZnO, ZrO ₂ , cobalt blue manufactured by CIK Nanotech, zirconium oxide, barium titanate, Titanium oxide, silica, alumina, MUA fillers.

Examples of organic fillers include: Techpolymer MBX series and SBX series manufactured by Sekisui Chemicals, Artpearl cross-linked acrylic beads manufactured by Negami Industries, Artpearl Crosslinked carbamate beads, Ganzpearl manufactured by Aica Kogyo.

These fillers can be used alone, or multiple fillers can be used in combination.

In the coating agent, other resin components may also be added. For example, thermoplastic resin and rubber can be mentioned.

By adding thermoplastic resin and rubber as other resins, the original properties of the resin (mechanical properties, surface, interface properties, compatibility, etc.) can be modified.

As the thermoplastic resin, for example, there are the following.

Polyethylene, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene resin, poly(meth)acrylate resin, ultra-high molecular weight Polyethylene, poly-4-methylpentene, syndiotactic polystyrene, polyacetal, polycarbonate, polyphenylene ether, polyphenylene sulfide, polysulfide, polyether sulfide, polyether ether ketone, polyarylate (U Polymer: Unitika (stock) trade name, Vectra: Polyplastics (stock) trade name, etc.), polyimide (card Kapton: Toray (Stock) trade name, AURUM: Mitsui Chemicals (Stock) trade name, etc.), polyetherimide and polyimideimide.

Polyamides such as nylon 6, nylon 6,6, nylon 6,10, nylon MXD6, nylon 6,T (all trade names: manufactured by DuPont Co., Ltd.).

Polyesters such as polyethylene terephthalate, polybutylene terephthalate, and polyethylene 2,6-naphthalene dicarboxylate.

Furthermore, fluororesin such as polytetrafluoroethylene and polyvinylidene fluoride.

The curable resin used for the surface layer 12 is used as a coating agent for coating on the base film. Therefore, the coating agent is preferably liquid. When the curable resin is solid, as described above, it only needs to be dissolved in a solvent and used as a coating agent.

The concentration of the curable resin in the coating agent can be selected so that the viscosity of the coating agent becomes corresponding to the viscosity of the coating method such as the wet coating method. The concentration is preferably 1wt%~80wt%, more preferably 3wt%~60wt%. The concentration of the curable resin in the coating agent can be adjusted by using a solvent. Solvents such as methyl ethyl ketone, General organic solvents such as methyl isobutyl ketone. Furthermore, when the solubility to a solvent is reduced by the length of the fluoroalkyl group contained in the fluorine compound contained in the curable composition, a fluorine-based organic solvent may be used. In addition, to the coating agent, other well-known additives such as leveling agents such as surfactants may be added as necessary. If a leveling agent is added, the surface tension of the coating agent can be controlled, and surface defects such as sags, pits, and the like during the formation of the layer can be suppressed.

Examples of the curing treatment for curing the curable resin include curing treatments such as ultraviolet irradiation, heating, and electron beam irradiation. Furthermore, when a solvent is contained in the coating film, it is generally preferable to heat the coating film in the range of 70°C to 200°C for several tens of minutes to remove the solvent remaining in the coating film, and then perform a curing treatment. As the curing by ultraviolet radiation, as long as it takes a short time (in the range of several seconds to several tens of seconds), it can be cured from ultraviolet (Ultraviolet, UV) lamps (such as high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, high-power metal halide lamps). Lamp) The coating liquid may be irradiated with ultraviolet light having a wavelength of 200 nm to 400 nm. In addition, as curing by electron beam irradiation, it is sufficient to irradiate the coating liquid with a low-energy electron beam from a self-shielding low-energy electron accelerator of 300 keV or less.

The fluorine-based compound (b) and the fluorosilsesquioxane derivative (c) have the property of being easy to accumulate on the interface between the air and the solid (or liquid) in a hydrophobic environment (for example, in the air). It is considered that this is because the components (b) and (c) containing a fluorine group have higher hydrophobicity than the resin, so they are attracted to the air side. Therefore, during the coating process, the components (b) and (c) gather in the vicinity of the surface of the surface layer 12, and the concentration of the components (b) and (c) is biased toward the surface side. As a result, as shown in Figures 1 and 2, the surface layer 12 In the vicinity of the surface, an inclined structure of the concentration of the (b) and (c) components is formed.

In addition, the components (b) and (c) have excellent characteristics as an antifouling material, and therefore can improve the antifouling properties of the surface of the surface layer 12.

[Laminated body 100, laminated body 200]

As shown in FIGS. 1 and 2, the laminate 100 and the laminate 200 according to the second embodiment of the present invention include a base film 11 having a surface layer 12 and an adhesive layer 13. The layered body 100 and the layered body 200 are provided with the release film 14 at the time of manufacture, but are used after the release film 14 is peeled off when attaching to the surface of an article as an adherend.

[Base Film 11]

As the base film 11, it is desirable to use a film formed of a thermoplastic resin.

Examples of thermoplastic resins include polyurethane resins, polyester resins, acetate resins, polyether ether resins, polycarbonate resins, polyamide resins, and polyimide resins. Resin, polyolefin resin, (meth)acrylic resin, polyvinyl chloride resin, polyvinylidene chloride resin, polystyrene resin, polyvinyl alcohol resin, polyarylate resin, polyphenylene sulfide Resins such as ether resins and norbornene resins. Specifically, it is preferably thermoplastic polyurethane, polycaprolactone (Polycaprolactone, PCL), acrylic polymer, polyester, polyacrylonitrile, polyetherketone, polystyrene, polyvinyl acetate, or These derivatives. These resins can be used alone, or multiple resins can be used in combination.

More preferably, it is a thermoplastic polyurethane. Examples of thermoplastic polyurethane include: Argotec 49510, Argotec 49510-DV, Nihon Matai manufactured by Argotec The company’s Esmer URPX86, Esmer URPX93, Esmer URSX98, and the DUS202, DUS213, DUS235, DUS501, DUS601, DUS605, DUS614, DUS203 manufactured by Sheedom , DUS220, DUS701, XUS2086, XUS2098, DUS451, DUS450, Unigrand XN2001, XN2002, XN2004 manufactured by Nihon Unipolymer Corporation. Among them, a polycaprolactone-based thermoplastic polyurethane using a polycaprolactone polyol as the polyhydroxy compound, or a polycarbonate-based thermoplastic polyamine using a polycarbonate polyol as the polyhydroxy compound is preferred. Formate or polyether-based thermoplastic polyurethane using polyether polyol as a polyhydroxy compound.

The film thickness of the base film 11 is not particularly limited, but when the invention of the present application is used as a laminate, the film thickness of the base film is preferably 25 μm to 300 μm, and more preferably 100 μm to 200 μm. If the film thickness of the base film is 25 μm or more, the mechanical strength of the base is sufficient, and a layer can be formed on the base. In addition, if the film thickness is 300 μm or less, the thickness of the laminate does not become too thick.

[Surface layer 12]

The surface layer 12 first applies a coating agent containing a curable composition to the surface of the base film 11. By drying. Harden to form the surface layer 12. In the surface layer 12, the (b) component and/or (c) component are gathered at the interface with air, and are comprised. In addition, "curable composition" is a crosslinking component (active ingredient) in a coating agent, and means (a) (b) (c) (d) component.

The film thickness of the surface layer 12 is typically 1 μm~100 μm, preferably 10 μm~ 50μm, more preferably 10μm~30μm. If the film thickness of the surface layer 12 is 1 μm or more, the mechanical strength is sufficient, and if the film thickness is 100 μm or less, the thickness of the laminate does not become too thick. Furthermore, when thermoplastic polyurethane is used for the base film, the film thickness of the surface layer 12 can be made thinner by virtue of the flexibility of the thermoplastic polyurethane. The preferred film thickness is 1 μm-50 μm, more preferably 3 μm-30 μm.

The coating of the coating agent containing the curable composition is preferably a wet coating method in which the curable composition is uniformly applied. As the wet coating method, a gravure coating method, a die coating method, or the like can be used.

The gravure coating method is a method of immersing a gravure roll with embossed engraving on the surface in a coating liquid, scraping off the coating agent adhering to the convex and concave portions on the surface of the gravure roll with a doctor blade, and accumulating the liquid in the concave portions. This can be accurately measured and transferred to the substrate. With the gravure coating method, the low-viscosity liquid can be coated thinly.

The die coating method is a method of applying pressure while extruding liquid from a coating nozzle called a die. By die coating method, high precision coating can be performed. Furthermore, since the liquid is not exposed to external air during coating, it is difficult to cause changes in the concentration of the coating agent due to drying, etc.

Examples of other wet coating methods include spin coating, bar coating, reverse coating, roll coating, slit coating, dipping, spray coating, kiss coating, and reverse kiss coating. Cloth method, air knife coating method, curtain coating method, rod coating method, etc. The method of coating can be appropriately selected from these methods in accordance with the required film thickness. Furthermore, by using a wet coating method, coating can be performed at a line speed of several tens of meters per minute (for example, about 20 m/min), and therefore, it can be manufactured in a large amount and the production efficiency can be improved.

[Adhesive layer 13/Release film 14]

As shown in FIGS. 1 and 2, the adhesive layer 13 is formed by applying an adhesive on the back side of the base film 11 that has been subjected to antifouling treatment (or antifouling treatment) by the surface layer 12. It may be formed directly on the surface of the base film 11, or may be laminated between the base film 11 via another layer.

As the adhesive used for the adhesive layer 13, acrylic adhesives, rubber adhesives, urethane adhesives, silicone adhesives, etc. can be used. In terms of product design, heat resistance is preferred for applications requiring long-term durability. Acrylic adhesive with excellent weather resistance.

Examples of acrylic adhesives include acrylic adhesives containing acrylic copolymers, which are copolymers of monomer components mainly composed of acrylate and monomer components having functional groups such as carboxyl groups or hydroxyl groups. Become.

Examples of acrylates include: methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and n-butyl (meth)acrylate , Isobutyl (meth)acrylate, second butyl (meth)acrylate, tertiary butyl (meth)acrylate, amyl (meth)acrylate, isoamyl (meth)acrylate, (meth) ) Hexyl acrylate, cyclohexyl (meth)acrylate, heptyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate Ester, nonyl (meth)acrylate, isononyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, undecyl (meth)acrylate, (meth)acrylic acid Lauryl ester, tridecyl (meth)acrylate, tetradecyl (meth)acrylate, pentadecyl (meth)acrylate, hexadecyl (meth)acrylate, heptadecyl (meth)acrylate, ( Stearyl meth)acrylate, (meth) Nonadecanyl acrylate, eicosanyl (meth)acrylate, isobornyl (meth)acrylate, 1-adamantyl (meth)acrylate, etc. One kind or two or more kinds of these alkyl (meth)acrylates can be used.

The alkyl (meth)acrylate can be copolymerized with the following monomer components. Examples of monomer components that can be copolymerized include itaconic acid, maleic acid, crotonic acid, isocrotonic acid, fumaric acid, (meth)acrylic acid, and carboxyethyl (meth)acrylate. , Carboxypentyl (meth)acrylate and other monomers containing carboxyl groups; 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, ( 6-hydroxyhexyl (meth)acrylate, 8-hydroxyoctyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, 12-hydroxylauryl (meth)acrylate, (4-hydroxymethyl)acrylate Monomers containing hydroxyl groups such as cyclohexyl)-methyl; glycidyl-containing monomers such as glycidyl (meth)acrylate and methylglycidyl (meth)acrylate; cyanogens such as acrylonitrile and methacrylonitrile -Based acrylate monomer; N,N-dimethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylamide, N,N-dimethyl (Meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, ( (Methyl) acryloyl morpholine, N-vinyl-2-piperidone, N-vinyl-3-morpholinone, N-vinyl-2-caprolactam, N-vinyl-2- Pyrolidone, N-vinyl-1,3-oxazin-2-one, N-vinyl-3,5-morpholinedione, N-cyclohexylmaleimide, N-phenyl Nitrogen-containing monomers such as maleimide, N-acryloylpyrrolidine, tertiary butylaminoethyl (meth)acrylate, styrene or styrene derivatives, vinyl acetate and other monomers Wait. If necessary, one or more of these monomers can be used after copolymerization with (meth)acrylate.

The adhesive used in the present invention preferably contains, for example, at least one selected from the group consisting of butyl acrylate and 2-ethylhexyl acrylate, and at least one selected from the group consisting of acrylic acid and methacrylic acid. At least one monomer containing carboxyl groups.

In order to improve heat resistance. For weather resistance, the adhesive used in the present invention adds hard components such as methyl acrylate and vinyl acetate to increase the glass transition temperature (Tg). Examples of hard components used for the adjustment of such glass transition temperature include methyl acrylate, vinyl acetate, methyl methacrylate, and acrylonitrile.

Furthermore, in order to further improve various physical properties such as weather resistance, ultraviolet absorbers, light stabilizers, etc. may be added as necessary.

The ratio of the hard component relative to the total amount of the adhesive is 10wt%~80wt%, preferably 20wt%~70wt%, more preferably 30wt%~60wt%.

The weight average molecular weight (Mw) of the acrylic copolymer is 50,000 to 2 million, preferably 100,000 to 1.5 million, more preferably 150,000 to 1 million.

The number average molecular weight (Mn) is 10,000 to 500,000, preferably 10,000 to 400,000, more preferably 10,000 to 300,000.

The dispersion value is 1-20, preferably 1-15, more preferably 2-10.

The glass transition temperature is -70°C to 0°C, preferably -40°C to 0°C, more preferably -30°C to 0°C, particularly preferably -20°C to 0°C.

When the composition that becomes the adhesive layer 13 is coated on the release film 14 or the base film 11, the usual gravure coating method, bar coating method, spray method, spin coating method, roll coating method, Die coating method, knife coating method, air knife coating method, hot melt coating method, curtain Painting method and so on.

In terms of adhesiveness after sticking, the thickness of the adhesive layer 13 is 10 μm to 100 μm, preferably 15 μm to 50 μm, and more preferably 25 μm to 45 μm.

As the release film 14, for example, plastic films such as polyester-based resins and polyolefin-based resins, cellophane, glassine paper, and other filled paper can be used. Furthermore, it is possible to use polyethylene terephthalate, polyethylene, polyethylene terephthalate, polyethylene terephthalate, polyethylene terephthalate, polyethylene terephthalate, fluorine-based resin, silicone-based resin, long-chain alkyl-containing urethane, etc. Polypropylene resin film, etc.

The thickness of the release film varies slightly depending on the material used, but is usually 10 μm to 250 μm, preferably 20 μm to 200 μm.

The laminate of the present application has excellent self-repairing properties and high water repellency due to the surface layer. Anti-fouling properties, and furthermore have elongation and smoothness. In addition, the surface layer can be used to smooth the surface, suppress reflectance, and have a gloss. In addition, the adhesive surface of the adhesive layer is protected by a peeling film with high releasability until it is attached to the adherend. Therefore, it is possible to circulate and transport without deteriorating the adhesiveness.

[Surface protection articles]

The surface protection article of the third embodiment of the present invention will be described. Examples of the article to which the laminated body of the present application is attached to the adherend include automobiles, airplanes, and ships. For the protection of various body parts of these items, especially those exposed to flying debris (such as sand, stones, etc.), insects and other dangerous parts (such as the front end of the front hood and other front end surfaces, rocking plates, etc.) The coating is effective.

Furthermore, it can be used for windows, building materials, digital signage, packaging, office Supplies, and can be used in a wide range of fields such as electronics, security, and industry. Furthermore, in the fields of nursing and medical treatment, it can also be applied to the packaging of waste, or the protection of the surface of medical equipment. In addition, the surface of the object to be protected can be smoothed, so the design can be improved.

[Example]

≪Test 1≫

[Production Example 1: Synthesis of (meth)acrylate urethane resin (a)]

Add 4,4'-dicyclohexylmethane diisocyanate (trade name: Desmodur (registered trademark), manufactured by Sumika Bayer Urethane (Stock)) 306g (1.2 Mol), polycarbonate diol using 1,4-cyclohexanedimethanol (trade name: ETERNACOLL (registered trademark) UC-100, manufactured by Ube Industries Co., Ltd.) 1000g (1 Mol), 1700 g of 2-butanone (MEK, methyl ethyl ketone) were reacted under the conditions of 70°C to 80°C, and the reaction was carried out until it became a predetermined residual isocyanate concentration. Then, 255 g (2.2 mol) of 2-hydroxyethyl acrylate (trade name: BHEA, manufactured by Nippon Shokubai Co., Ltd.) and hydroquinone monomethyl ether (trade name: MQ, After 0.85 g of Kawaguchi Chemical Industry Co., Ltd.), the reaction was further carried out at 70°C to 80°C until the residual isocyanate concentration became 0.1% by weight to obtain a polycarbonate acrylic urethane resin (a) . Furthermore, 642 g of MEK was added, and the solid content concentration was adjusted to 40 wt%. The weight average molecular weight of the obtained polymer determined by Gel Permeation Chromatography (GPC) analysis was 100,000.

[Production Example 2: Synthesis of fluorine compound (b) having polymerizable functional group]

In a nitrogen environment, and at room temperature, the perfluoropolyether is made by Solvay Solexis (Fomblin Zdol)-4000 (average molecular weight is 4000). 50g was dissolved in hexafluoro-m-xylene (70g), and 3.5g of propylene oxyethyl isocyanate (trade name: Karenz AOI, manufactured by Showa Denko Corporation) was added to it, and then Heat to 45°C in a nitrogen atmosphere. A solution of 0.076 g of dibutyltin dilaurate (manufactured by Tokyo Chemical Industry Co., Ltd.) dissolved in 0.55 g of methyl ethyl ketone (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise, and the temperature was kept at 45°C to 50°C. Stir for 2 hours. Furthermore, a solution prepared by dissolving 0.043 g of dibutyltin dilaurate (manufactured by Tokyo Chemical Industry Co., Ltd.) in 0.55 g of methyl ethyl ketone (manufactured by Wako Pure Chemical Industries, Ltd.) was added, and stirred at this temperature for 2 hour. After that, the reaction liquid was cooled in an ice bath, and methanol (2.0 g) was added dropwise. It stirred at this temperature for 30 minutes, and diluted with methyl ethyl ketone (7.4g), and obtained the solution of the perfluoropolyether compound (b) which has a polymerizable functional group at both ends. (134g solid content is 40wt%)

[Production Example 3: Synthesis of fluorosilsesquioxane derivative (c); Synthesis of polymer A-1]

The following compound A (25g), Silaplane FM0721 (6.3g, manufactured by JNC (Co., Ltd.)), methyl group were added to a nitrogen-sealed four-necked round bottom flask equipped with a reflux device and a dropping funnel. 2-Hydroxyethyl acrylate (18.8g), methyl methacrylate (12.5g), and methyl ethyl ketone (62g) were refluxed for 15 minutes in an oil bath. After deaeration, a solution prepared by dissolving azobisisobutyronitrile (0.48 g) and thioglycolic acid (0.054 g) in methyl ethyl ketone (4.8 g) was introduced to start polymerization. Three hours after the start of the polymerization, azobisisobutyronitrile (0.48 g) was dissolved in methyl ethyl ketone (4.3 g) and added, and aged for 5 hours to obtain a solution of the obtained copolymer. Furthermore, p-methoxyphenol (0.16g) as a polymerization inhibitor and dibutyltin dilaurate (0.15g, manufactured by Showa Denko Corporation) were dissolved in methyl ethyl ketone (1.5g) and added. , Using a dropping funnel to drop Karenz AOI (26.4 g) so that the liquid temperature was changed from 35°C to 50°C, and then aged at 45°C for 3 hours after dropping.

After that, methanol (9g) was added for treatment, and then p-methoxyphenol (0.16g) was added, and it was diluted with methyl isobutyl ketone (107.3g) to obtain the target polymer (A-1) 30wt% solution.

The weight average molecular weight of the obtained polymer (A-1): Mw was 42,000, and the polydispersity index: Mw/Mn was 1.9. The weight average molecular weight and polydispersity index are measured by gel permeation chromatography (GPC, model: Alliance 2695, manufactured by Waters), column: Shodex GPC KF-804L×2 ( Series), protection column: KF-G) to determine.

Compound A has a molecular structure represented by the following formula (5).

[化6]

[Production Example 4: Preparation of Coating Agent A]

Combine Purple UV1700B (100wt% solid content, molecular weight 2,000, manufactured by Nippon Synthetic Chemical Co., Ltd.) 30g, methyl isobutyl ketone 68.5g, photopolymerization initiator (d) (trade name: Irgacure ) 184, made by BASF) 1.5 g was added to a 0.3L-scale stainless steel bottle and stirred with a stirring blade for 1 hour to obtain coating agent A with a solid content (active ingredient (a')) of 30 wt%. Coating agent A contains a monomer of acrylic urethane.

[Production Example 5: Preparation of Coating Agent B]

(Meth)acrylate urethane resin (a) 75g, methyl isobutyl ketone 23.5g, photopolymerization initiator (d) (trade name: Irgacure 184, manufactured by BASF ) 1.5 g was added to a 0.3L-scale stainless steel bottle, and stirred with a stirring blade for 1 hour to obtain coating agent B with a solid content (active ingredient (a)) of 30 wt%. Coating agent B contains (a) component.

[Production Example 6: Preparation of Coating Agent C]

(Meth) acrylic urethane resin (a) 71.3 g, fluorine compound (b) 3.8 g, methyl isobutyl ketone 23.6 g, photopolymerization initiator (d) (trade name: 1.5 g of Irgacure 184 (manufactured by BASF) was added to a 0.3L-scale stainless steel bottle, and stirred with a stirring blade for 1 hour, to obtain a solid content (active ingredient (a) (b)) of 30 wt%的coating agent C. Coating agent C contains (a) and (b) components.

[Production Example 7: Preparation of Coating Agent D]

(Meth) acrylic urethane resin (a) 74.3 g, fluorosilsesquioxane derivative (c) 1 g, methyl isobutyl ketone 23.3 g, photopolymerization initiator (d) ( Trade name: Irgacure 184 (manufactured by BASF) 1.5 g was added to a 0.3L-scale stainless steel bottle, and stirred with a stirring blade for 1 hour to obtain solid content (active ingredients (a) (c)) It is 30wt% coating agent D. Coating agent D contains (a) and (c) components.

[Production Example 8: Preparation of Coating Agent E]

(Meth) acrylic urethane resin (a) 70.5g, fluorine compound (b) 3.8g, fluorosilsesquioxane derivative (c) 1g, methyl isobutyl ketone 23.3g, 1.5 g of the photopolymerization initiator (d) (trade name: Irgacure 184, manufactured by BASF) was added to a 0.3L-scale stainless steel bottle, and stirred with a stirring blade for 1 hour to obtain a solid component ( The active ingredient (a), (b), and (c)) is 30wt% coating agent E. Coating agent E contains (a), (b), and (c) components.

[Production Example 9: Preparation of Adhesive A]

To a copolymer containing 40 parts by weight to 55 parts by weight of butyl acrylate, 40 parts by weight to 55 parts by weight of methyl acrylate, 1 part by weight to 15 parts by weight of vinyl acetate, and 0.1 part by weight to 3 parts by weight of carboxyl group-containing acrylate Namely add to acrylic adhesive A Add 30 parts by weight of ethyl acetate, and use a stirring blade to stir at 23° C. for 30 minutes to adjust the solid content to 23 wt% and the viscosity to be 1000 CPS. The weight average molecular weight (Mw) of the adhesive A is 550,000, and the glass transition temperature is -16°C.

[Example 1: Preparation of laminate 1]

Thermoplastic polyurethane film (trade name: Argotec (Argotec) 49510, manufactured by Argotec) with a 50μm polyethylene terephthalate protective film on one side, thickness 6mil= 152.4 μm) thermoplastic polyurethane film, coated with the prepared adhesive A by die coating, and dried at 70° C.×3 minutes to form an adhesive layer of 30 μm. Furthermore, a 75μm-thick polyethylene terephthalate film (release film A, surface roughness 716nm) that has been peeled off with a silicone resin is crimped onto the adhesive layer using a rubber roller, and Cure for 1 day in an environment of 45°C. After that, the 50 μm polyethylene terephthalate protective film was peeled off, and the coating agent C was applied to the surface using a coating rod No. 8 (manufactured by RDS Webster), and Drying was performed under the conditions of 90°C×3 minutes. After that, a conveyor-type ultraviolet irradiation device equipped with a H-bulb manufactured by Fusion was used for light curing (cumulative light quantity: 850mJ/cm ² ) to obtain a surface with a coating film thickness of 5 μm Layered laminated body 1.

[Example 2: Preparation of laminate 2]

The layered product 2 was obtained in the same manner as the layered product 1 except that the coating agent E was used instead of the coating agent C.

[Comparative Example 1: Preparation of Layered Body 3]

Thermoplastic polyurethane film (trade name: Argotec (Argotec) 49510, manufactured by Argotec) with a 50μm polyethylene terephthalate protective film on one side, thickness 6mil= 152.4 μm) thermoplastic polyurethane film, coated with the prepared adhesive A by die coating, and dried at 70° C.×3 minutes to form an adhesive layer of 30 μm. Furthermore, a 75μm-thick polyethylene terephthalate film (release film A, surface roughness 716nm) that has been peeled off with a silicone resin is crimped onto the adhesive layer using a rubber roller, and Curing was performed for one day in an environment of 45° C. to obtain a laminate 3.

[Comparative Example 2: Preparation of Layered Body 4]

The layered product 4 was obtained in the same manner as the layered product 1 except that the coating agent A was used instead of the coating agent C.

[Comparative Example 3: Preparation of Layered Body 5]

The layered product 5 was obtained in the same manner as the layered product 1 except that the coating agent B was used instead of the coating agent C.

[Comparative Example 4: Preparation of Layered Body 6]

A layered body 6 was obtained in the same manner as the layered body 1 except that the coating agent D was used instead of the coating agent C.

[experiment method]

(1) Self-healing: brass brush damage recovery test

Peel off the peeling film of the laminate cut to a size of 40mm in width and 130mm in length, and mix it with 1L of water by spraying Baby Shampoo (Baby Body Body Wash, manufactured by Johnson & Johnson) 2 ~3 drops The resulting aqueous solution is blown onto the adhesive layer side, surface, and coating board (width 50mm, length 150mm, thickness 1.2mm) coated with black paint for automobiles, and uses a rubber scraper to squeeze out bubbles and water bubbles. , Attach the adhesive layer of the laminate to the coating board on one side. After that, it was left at room temperature until the bubbles and water bubbles remaining in the adhesive layer and the coating plate disappeared visually, thereby obtaining a sample. The self-repair test uses 4 rows of brass brushes (AS ONE), with a load of 1000kgf, a speed of 3000mm/min, a distance of 100mm each way, and 10 round trips (HEIDON Type): After rubbing the surface of the test piece with 14W Shinto Science (Co., Ltd.), quickly remove the brass brush and observe the time until the scratches formed on the surface disappear.

○: The scratches disappeared within 1 minute.

×: The scratches did not disappear even after 1 minute.

(2) Water repellency: measurement of contact angle

For the surface layer of the laminate, distilled water (for nitrogen and phosphorus measurement, manufactured by Kanto Chemical Co., Ltd.) was used as the probe liquid, and the surface of the laminate was measured with a contact angle meter (Drop Master 400, manufactured by Kyowa Interface Science Co., Ltd.) The contact angle of the layer of water.

(3) Antifouling property (oil repellency): wipe test with magic ink

Use a black oil-based marker (manufactured by Sharpie) to trace the surface layer of the laminate, and evaluate the repellency of oil-based ink, and use Dusper K-3 (manufactured by Ozu Sangyo Co., Ltd.) ) Of the erasure.

○: The ink is repelled and wiped off cleanly.

×: Cannot be wiped off.

(4) Elongation: elongation at break in tensile test

The release film of the laminate cut into a size of 35 mm in width and 200 mm in length was peeled off and set in a tensile testing machine (Strograph VG, Toyo Seiki Seisakusho Co., Ltd.) so that the distance between the chucks becomes 100 mm. ) The upper and lower crossheads of) were then moved upward at a crosshead speed of 127 mm/min. The movement distance of the cracks on the surface was visually measured, and the elongation at break was calculated by the following formula.

Elongation at break (%) = moving distance of cross head (mm) / distance between chucks (mm) × 100

(5) Smoothness: Scraper sliding test

Peel off the release film of the laminate cut into a size of 40mm in width and 130mm in length, and mix 2 to 3 drops of baby shower gel (baby body shower gel, manufactured by Johnson & Johnson) in 1L of water by spraying. Blow on the adhesive layer side, the surface, and the coating board (width 50mm, length 150mm, thickness 1.2mm) coated with automotive black paint, and use a rubber scraper to squeeze out air bubbles and water bubbles, and the laminated body The adhesive layer is attached to the coating board.

○: Attached smoothly.

×: A stuck part occurred.

With the formulations of Example 1 and Example 2, self-healing properties, water and oil repellency (anti-fouling properties), and elongation properties coexist. In addition, in Example 2, the smoothness of the surface is further improved.

≪Test 2≫

[Production Example 10: Preparation of Coating Agent F]

(Meth) acrylic urethane resin (a) 74.2 g, fluorine compound (b) 0.1 g, methyl isobutyl ketone 23.3 g, photopolymerization initiator (d) (trade name: Yan 1.5 g of Irgacure 184 (manufactured by BASF) was added to a 0.3L-scale stainless steel bottle and stirred with a stirring blade for 1 hour to obtain a solid content (active ingredient (a) (b)) of 30 wt% Coating agent F. Coating agent F contains (a) (b) Ingredients.

[Production Example 11: Preparation of Coating Agent G]

(Meth) acrylic urethane resin (a) 73.5 g, fluorine compound (b) 0.8 g, methyl isobutyl ketone 23.3 g, photopolymerization initiator (d) (trade name: Yan 1.5 g of Irgacure 184 (manufactured by BASF) was added to a 0.3L-scale stainless steel bottle and stirred with a stirring blade for 1 hour to obtain a solid content (active ingredient (a) (b)) of 30 wt% Coating agent G. Coating agent G contains (a) and (b) components.

[Production Example 12: Preparation of Coating Agent H]

(Meth) acrylic urethane resin (a) 69.0 g, fluorine compound (b) 5.3 g, methyl isobutyl ketone 23.4 g, photopolymerization initiator (d) (trade name: Yan 1.5 g of Irgacure 184 (manufactured by BASF) was added to a 0.3L-scale stainless steel bottle and stirred with a stirring blade for 1 hour to obtain a solid content (active ingredient (a) (b)) of 30 wt% Coating agent H. Coating agent H contains (a) and (b) components.

[Production Example 13: Preparation of Coating Agent I]

(Meth) acrylic urethane resin (a) 66.8 g, fluorine compound (b) 7.5 g, methyl isobutyl ketone 23.4 g, photopolymerization initiator (d) (trade name: Yan 1.5 g of Irgacure 184 (manufactured by BASF) was added to a 0.3L-scale stainless steel bottle and stirred with a stirring blade for 1 hour to obtain a solid content (active ingredient (a) (b)) of 30 wt% Coating agent I. Coating agent I contains (a) and (b) components.

[Example 3: Preparation of laminate 7]

A layered body 7 was obtained in the same manner as the layered body 1 except that the coating agent F was used instead of the coating agent C.

[Example 4: Preparation of laminate 8]

The layered body 8 was obtained in the same manner as the layered body 1 except that the coating agent G was used instead of the coating agent C.

[Example 5: Preparation of laminate 9]

A layered body 9 was obtained in the same manner as the layered body 1 except that the coating agent H was used instead of the coating agent C.

[Example 6: Preparation of laminate 10]

The layered body 10 was obtained in the same manner as the layered body 1 except that the coating agent I was used instead of the coating agent C.

[experiment method]

Set the test method to be the same as ≪Test 1≫.

In the weight ratio ((a):(b)) of the (a) component (b), the performance is exhibited when the ratio of the component (b) is 1 part by weight to 7 parts by weight.

≪Test 3≫

[Production Example 14: Preparation of Coating Agent J]

(Meth) acrylic urethane resin (a) 71.2g, fluorine compound (b) 3.8g, fluorosilsesquioxane derivative (c) 0.01g, methyl isobutyl ketone 23.6g , Photopolymerization initiator (d) (trade name: Irgacure 184, manufactured by BASF) 1.5g was added to a 0.3L-scale stainless steel bottle, and stirred with a stirring blade for 1 hour to obtain solid content (Active ingredient (a), (b), and (c)) Coating agent J of 30 wt%. Coating agent J contains (a), (b), and (c) components.

[Production Example 15: Preparation of Coating Agent K]

(Meth) acrylic urethane resin (a) 71.2g, fluorine compound (b) 3.8g, fluorosilsesquioxane derivative (c) 0.1g, methyl isobutyl ketone 23.6g , Photopolymerization initiator (d) (trade name: Irgacure 184, manufactured by BASF) 1.5g was added to a 0.3L-scale stainless steel bottle, and stirred with a stirring blade for 1 hour to obtain solid content (Active ingredient (a), (b), and (c)) Coating agent K is 30 wt%. Coating agent K contains (a), (b), and (c) components.

[Production Example 16: Preparation of Coating Agent L]

(Meth) acrylic urethane resin (a) 69.0g, fluorine compound (b) 3.8g, fluorosilsesquioxane derivative (c) 3g, methyl isobutyl ketone 22.9g, 1.5 g of the photopolymerization initiator (d) (trade name: Irgacure 184, manufactured by BASF) was added to a 0.3L-scale stainless steel bottle, and stirred with a stirring blade for 1 hour to obtain a solid component ( The active ingredient (a), (b), (c)) is 30 wt% of coating agent L. The coating agent L contains (a), (b), and (c) components.

[Production Example 17: Preparation of Coating Agent M]

(Meth) acrylic urethane resin (a) 67.5g, fluorine compound (b) 3.8g, fluorosilsesquioxane derivative (c) 5g, methyl isobutyl ketone 22.4g, 1.5 g of the photopolymerization initiator (d) (trade name: Irgacure 184, manufactured by BASF) was added to a 0.3L-scale stainless steel bottle, and stirred with a stirring blade for 1 hour to obtain a solid component ( The active ingredient (a), (b), (c)) is 30 wt% of the coating agent M. The coating agent M contains (a), (b), and (c) components.

[Example 7: Preparation of laminate 11]

The layered body 11 was obtained in the same manner as the layered body 2 except that the coating agent J was used instead of the coating agent E.

[Example 8: Preparation of laminate 12]

The layered body 12 was obtained in the same manner as the layered body 2 except that the coating agent K was used instead of the coating agent E.

[Example 9: Preparation of laminate 13]

The layered body 13 was obtained in the same manner as the layered body 2 except that the coating agent L was used instead of the coating agent E.

[Example 10: Preparation of laminate 14]

The layered body 14 was obtained in the same manner as the layered body 2 except that the coating agent M was used instead of the coating agent E.

[experiment method]

Set the test method to be the same as ≪Test 1≫.

In the weight ratio ((a):(b):(c)) of (a)(b)(c) component, when the ratio of (c) component is 0.1 weight part-5 weight part, it will exhibit performance.

≪Test 4≫

[Example 11: Preparation of laminate 15]

Except for using the coating rod No. 4 instead of the coating rod No. 8, a layered body 15 having a coating film thickness of 3 μm was obtained in the same manner as the layered body 2.

[Example 12: Preparation of laminate 16]

Except for using the coating rod No. 16 instead of the coating rod No. 8, a layered body 16 having a coating film thickness of 10 μm was obtained in the same manner as the layered body 2.

[Example 13: Preparation of laminate 17]

Except for using the coating rod No. 30 instead of the coating rod No. 8, a layered body 17 with a coating film thickness of 20 μm was obtained in the same manner as the layered body 2.

[Example 14: Preparation of laminate 18]

Except that the coating rod No. 55 was used instead of the coating rod No. 8, a layered body 18 with a coating film thickness of 30 μm was obtained in the same manner as the layered body 2.

[experiment method]

Set the test method to be the same as ≪Test 1≫.

Performance is exhibited when the film thickness of the surface layer is 5 μm or more.

≪Test 5≫

[Production Example 18: Preparation of Coating Agent N]

(Meth) acrylic urethane resin (a) 70.5g, fluorine compound (b) 3.8g, fluorosilsesquioxane derivative (c) 1g, methyl isobutyl ketone 20.4g, Photopolymerization initiator (d) (trade name: Irgacure 184, manufactured by BASF) 1.5 g, ultraviolet absorber (f) (trade name: TINUVIN) 384-2, manufactured by BASF , Solid content is 95wt%) 3g is added to a 0.3L-scale stainless steel bottle, and stirred with a stirring blade for 1 hour to obtain a coating with a solid content of 30wt% (active ingredients (a)(b)(c))剂 N. Coating agent N contains (a), (b), (c), and (f) components.

[Production Example 19: Preparation of Coating Agent O]

(Meth) acrylic urethane resin (a) 70.5g, fluorine compound (b) 3.8g, fluorosilsesquioxane derivative (c) 1g, methyl isobutyl ketone 20.4g, Photopolymerization initiator (d) (trade name: Irgacure 184, manufactured by BASF) 1.5 g, light stabilizer (f) (trade name: TINUVIN 292, manufactured by BASF, solid 100wt% of ingredients) 2.8g was added to a 0.3L scale stainless steel bottle, and stirred with a stirring blade for 1 hour to obtain a coating agent with a solid content (active ingredients (a), (b), (c)) of 30wt% O. Coating agent O contains (a), (b), (c), and (f) components.

[Production Example 20: Preparation of Coating Agent P]

(Meth) acrylic urethane resin (a) 70.5g, fluorine compound (b) 3.8g, fluorosilsesquioxane derivative (c) 1g, methyl isobutyl ketone 4.5g, Photopolymerization initiator (d) (trade name: Irgacure 184, manufactured by BASF) 1.5 g, inorganic filler (f) (trade name: Cobalt Blue, CIK Nano Technology Corporation) The solid content is 15wt%) 18.8g is added to a 0.3L-scale stainless steel bottle, and stirred with a stirring blade for 1 hour, and the solid content (active ingredients (a)(b)(c)) obtained is 30wt%的coating agent P. Coating agent P contains (a), (b), (c), and (f) components.

[Production Example 21: Preparation of Coating Agent Q]

(Meth) acrylic urethane resin (a) 70.5g, fluorine compound (b) 3.8g, fluorosilsesquioxane derivative (c) 1g, methyl isobutyl ketone 17.6g, Photopolymerization initiator (d) (trade name: Irgacure 184, manufactured by BASF) 1.5 g, ultraviolet absorber (f) (trade name: TINUVIN) 384-2, manufactured by BASF , Solid content is 95wt%) 3g, light stabilizer (f) (trade name: TINUVIN 292, made by BASF, solid content is 100wt%) 2.8g is added to a 0.3L scale stainless steel bottle, It was stirred with a stirring blade for 1 hour to obtain a coating agent Q having a solid content (active ingredients (a), (b) (c)) of 30 wt%. Coating agent Q contains (a), (b), (c), and (f) components.

[Production Example 22: Preparation of Coating Agent R]

(Meth) acrylic urethane resin (a) 70.5g, fluorine compound (b) 3.8g, fluorosilsesquioxane derivative (c) 1g, methyl isobutyl ketone 0.1g, Photopolymerization initiator (d) (trade name: Irgacure 184, manufactured by BASF) 1.5 g, ultraviolet absorber (f) (trade name: TINUVIN) 384-2, manufactured by BASF , Solid content 95wt%) 3g, light stabilizer (f) (trade name: TINUVIN 292, manufactured by BASF, solid content 100wt%) 2.8g, inorganic filler (f) (trade name: cobalt Blue, CIK Nano Technology Made by the company, solid content is 15wt%) 18.8g is added to a 0.3L scale stainless steel bottle, and stirred with a stirring blade for 1 hour, and the solid content (active ingredients (a)(b)(c)) obtained is 30wt%的coating agent R. Coating agent R contains (a), (b), (c), and (f) components.

[Example 15: Preparation of laminate 19]

The layered body 19 was obtained in the same manner as the layered body 2 except that the coating agent N was used instead of the coating agent E.

[Example 16: Preparation of laminate 20]

The layered body 20 was obtained in the same manner as the layered body 2 except that the coating agent O was used instead of the coating agent E.

[Example 17: Preparation of laminate 21]

The layered body 21 was obtained in the same manner as the layered body 2 except that the coating agent P was used instead of the coating agent E.

[Example 18: Preparation of laminate 22]

The layered body 22 was obtained in the same manner as the layered body 2 except that the coating agent Q was used instead of the coating agent E.

[Example 19: Preparation of laminate 23]

The layered body 23 was obtained in the same manner as the layered body 2 except that the coating agent R was used instead of the coating agent E.

[experiment method]

Set the test method to be the same as ≪Test 1≫.

[table 5]

Even when the component (f) is added, there is no influence on self-healing properties, water and oil repellency (antifouling properties), elongation, and surface smoothness.

≪Test 6≫

[Example 20: Preparation of laminate 24]

Except for the use of thermoplastic polyurethane film (trade name: Esmer (Esmer) URS PX98, manufactured by Japan Matai Company, with a thickness of 150μm) instead of thermoplastic polyurethane film (trade name: Argotec (Argotec) 49510, manufactured by Argotec, thickness 6mil=152.4 μm), a layered body 24 was obtained in the same manner as the layered body 2.

[Example 21: Preparation of laminate 25]

Except for the use of thermoplastic polyurethane film (trade name: XUS2098, manufactured by Siden, with a thickness of 150μm) instead of thermoplastic polyurethane film (trade name: Argotec 49510, Argotec The laminated body 25 was obtained in the same manner as the laminated body 2 except that the thickness was 6mil=152.4 μm) manufactured by the company.

[Example 22: Preparation of laminate 26]

Except for the use of thermoplastic polyurethane film (trade name: DUS451, manufactured by Seadon, with a thickness of 150μm) instead of thermoplastic polyurethane film (trade name: Argotec (Argotec) 49510, Argotec The laminated body 26 was obtained in the same manner as the laminated body 2 except that the thickness was 6mil=152.4 μm) manufactured by the company.

[Comparative Example 5: Preparation of Layered Body 27]

In addition to using polyester film (trade name: Lumirror (Lumirror) T60, manufactured by Toray, with a thickness of 125 μm) instead of thermoplastic polyurethane film (trade name: Argotec 49510, Argotec The laminated body 27 was obtained in the same manner as the laminated body 2 except for the thickness of 6 mil = 152.4 μm) manufactured by Tektronix.

[experiment method]

Set the test method to be the same as ≪Test 1≫.

If a thermoplastic polyurethane film is used for the substrate, a laminate with good extensibility can be obtained regardless of the type.

≪Test 7≫

[Production example 23: Production of adherend A]

Using sandpaper (#800), one side of a polycarbonate sheet (trade name: PC1151, manufactured by Teijin Co., Ltd., Panlite thickness: 2 mm, width: 70 mm, and length: 150 mm) was damaged to produce an adherend A.

[Example 23: Preparation of test body A]

The peeling film of the laminate 2 cut to a size of 40 mm in width and 130 mm in length is peeled off, and an aqueous solution of 2 to 3 drops of baby shower gel (baby body shower gel, manufactured by Johnson & Johnson) mixed with 1L of water by spraying Towards the adhesive layer side, surface And polycarbonate sheet (trade name: PC1151, manufactured by Teijin Co., Ltd., Panlite thickness: 2mm, width: 70mm, length: 150mm) blown on, and air bubbles and water bubbles are extruded with a rubber scraper on one side The adhesive layer of the laminate was stuck on a polycarbonate sheet to produce a test body A.

[Example 24: Preparation of test body B]

Except that the adherend A was used instead of the polycarbonate sheet (trade name: PC1151, manufactured by Teijin, Panlite thickness: 2mm, width: 70mm, length: 150mm), a test was made in the same manner as in Example 23 Body B.

[experiment method]

(1) Optical characteristics: total light transmittance and haze

Using a haze meter (Suga Test Instruments Hz-2), a sample pressing plate was installed on the opening side of the integrating sphere in the sample measurement chamber, and the total light transmittance and haze were measured. (JIS K7105)

(2) Durability: burst test

Using a simple chipping tester (made by JNC), 50 g of crushed stone (No. 7) was collided at a speed of 40 km per hour, and the appearance of the substrate was visually confirmed. When the laminate is attached to the substrate, the appearance is confirmed after peeling the film from the substrate.

○: No damage

×: Damaged

Since the surface can be smoothed by attaching the laminate, the haze value is reduced and the design of the adherend is improved. In addition, by attaching the laminate, the substrate can be protected and the durability can be improved.

Each document is individually and concretely shown and incorporated by reference to the same extent. In addition, to the same extent as the entire content is described in this specification, reference includes publications, patent applications, and references cited in this specification. All patent documents are incorporated into this specification.

As long as it is not specifically pointed out in this specification or is not clearly inconsistent with the context, the use of nouns and the same indicator used in connection with the description of the present invention (especially related to the scope of the following patent applications) is interpreted as It involves the use of both the singular and the plural. As long as there is no special explanation in advance, the words "have", "have", "contain" and "include" shall be interpreted as open-ended thesaurus (that is, the meaning of "include ~, but not limited"). As long as it is not specifically pointed out in this specification, the detailed description of the numerical range in this specification is only intended to serve as a notation for individually discussing each value within its range, and each value is as individual in this specification Enumerated It is incorporated into the manual. As long as it is not specifically pointed out in this specification or is not obviously inconsistent with the context, all the methods described in this specification can be performed in all appropriate orders. As long as there is no special claim, all examples or exemplified words (such as "etc.") used in this specification are only intended to better describe the present invention, and are not intended to limit the scope of the present invention. Any wording in the specification is not to be construed as a wording that is indispensable in the implementation of the present invention and represents an element not described in the scope of the patent application.

In this specification, in order to implement the present invention, preferred embodiments of the present invention including the best mode known to the inventors have been described. For those skilled in the art, after reading the description, the deformation of these preferred embodiments will become clear. The inventors of the present invention anticipate that those skilled in the art can suitably apply such modifications, and expect to implement the present invention in methods other than those specifically described in this specification. Therefore, as permitted by the applicable law, the present invention includes all changes and equivalents of the content described in the scope of patent application attached to this specification. Furthermore, as long as it is not specifically pointed out in this specification, or is not clearly contradictory to the context, any combination of the aforementioned elements in all modifications is also included in the present invention.

11‧‧‧Base film

12‧‧‧Surface layer

13‧‧‧Adhesive layer

14‧‧‧Peeling film

100‧‧‧Layered body

fc‧‧‧Fluorine compound

s1‧‧‧surface

Claims (9)

A coating agent comprising a (meth)acrylate urethane resin (a), a fluorine compound (b), and a photopolymerization initiator (d). The (meth)acrylate urethane resin The acid ester resin (a) has a weight average molecular weight (Mw) of 10,000 to 800,000, and the fluorine-based compound (b) has at least two polymerizable functional groups, relative to the (meth)acrylic urethane carboxylic acid The total amount of the ester resin (a) and the fluorine compound (b) contains 1 wt% to 9 wt% of the fluorine compound (b). The coating agent according to the first item of the patent application, wherein the fluorine-based compound (b) is a perfluoropolyether having a (meth)acryloyl group. The coating agent as described in item 1 of the scope of the patent application, which further includes a fluorosilsesquioxane derivative (c), and the fluorosilsesquioxane derivative (c) has at least one polymerizable functional group . The coating agent according to item 3 of the scope of patent application, wherein the fluorosilsesquioxane derivative (c) is a cage structure fluorosilsesquioxane. The coating agent according to item 3 or item 4 of the scope of patent application, wherein the (meth)acrylate urethane resin (a), the fluorine compound (b), the The total amount of the fluorosilsesquioxane derivative (c) contains 0.1 wt% to 10 wt% of the fluorosilsesquioxane derivative (c). A coating film obtained by hardening the coating agent described in any one of the first to the fifth claims. A laminated body, which includes: The base film is formed of thermoplastic polyurethane; and the surface layer is formed by applying the coating agent described in any one of items 1 to 5 in the scope of the patent application to the base film One side is hardened and formed. The laminate according to claim 7, wherein an adhesive layer is provided on the side opposite to the first surface side of the base film, and peeling is provided on the side of the adhesive layer opposite to the base film A film, the adhesive layer contains at least one resin selected from the group consisting of acrylic, urethane, rubber, and silicone, and is coated on the surface of the release film facing the adhesive layer There is at least one release agent selected from fluorine resins, silicone resins, and long-chain urethanes. A surface protection article, comprising: the laminated body described in the scope of patent application from which the peeling film is peeled off; and the laminated body from which the peeling film is peeled off is attached to the surface by the adhesive layer article.

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